Method of dyeing synthetic fibers and blends

ABSTRACT

A METHOD OF DYEING A TEXTILE FIBER SELECTED FROM THE GROUP CONSISTING OF A MODIFIED POLYESTER,POLYVINYL CHLORIDE,POLYACRYLONITRILE AND CELLULOSE ACTETATE FIBERS,WHICH COMPRISES DYEING THE FIBERS WITHAN ANIONIC DYESTUFF IN THE PRESENCE OF ATLEAST ONE COMPOUNDSELECTEDFROMSULFONIUM SALTSOF THE FORMULA   (R-S(-R1)-R2)(+) X(-) OR (R-O-R3-S(-R1)-R4-O-R2)(+) X(-)   WHEREIN R, R1 AND R2 ARE EACH SELECTED FROM THE GROUP CONSISTING OF ALKYL, ALKENYL, CYCLOALKYL, ARYL AND ARALKYL GROUPS OF 1-18 CARBON ATOMS, R3 AND R4 ARE EACH ALKYL GROUPS OF 1-5 CARBON ATOMS AND X IS SELECTED FROM THE GROUP CONSISTING OF HALOGENS, ALKOXY SULFATE AND OH GROUP.

United States Patent Oflice 3,826,609 METHOD OF DYEING SYNTHETIC FIBERSAND BLENDS Shiro Shimauchi, Norihiro Minemura, Takeshi Matsui, and KenjiIto, Osaka, and Takeo Shima, Shoji Kawase, and Masataka Oshima, Iwakuni,Japan, assignors to Teijin Limited, Osaka, Japan No Drawing. Originalapplication Mar. 4, 1969, Ser. No. 804.294, now Patent No. 3,666,403.Divided and this application May 16, 1972, Ser. No. 253,767

Int. Cl. D06p 3/82, N76

US. Cl. 8-21 R Claims ABSTRACT OF THE DISCLOSURE .A method of dyeing atextile fiber selected from the group consisting of a modifiedpolyester, polyvinyl chloride, polyacrylonitrile and cellulose acetatefibers, which comprises dyeing the fibers with an anionic dyestufr inthe presence of at least one compound selected from sulfonium salts ofthe formula wherein R, R and R are each selected from the groupconsisting of alkyl, alkenyl, cycloalkyl, aryl and aralkyl groups of1-18 carbon atoms, R and R are each alkyl groups of 1-5 carbon atoms andX is selected from the group consisting of halogens, alkoxy sulfate andOH group.

wherein R, R and R are each selected from the group consisting of alkyl,alkenyl, cycloalkyl, aryl and aralkyl groups of l-18 carbon atoms, R andR are each alkyl groups of 1-5 carbon atoms and X is selected from thegroup consisting of halogens, alkoxy sulfate and OH group.

Fibers manufactured from such synthetic polyesters as polyethyleneterephthalate do not have any aflinity at all for the ionic dyestuffsand, accordingly, they were previously dyed principally by means ofdisperse dyes. However, disperse dyes are costly and moreover the dyedproducts obtained by their use were not satisfactory with respect tobrightness. Therefore, there was a strong demand in the trade for themodification of the polyester fibers so that they could be dyed by meansof ionic dyestuffs, particularly acid dyes. It is therefore a primaryobject of this invention to provide a method by which modified polyestercan be dyed to deep shades.

Numerous methods of dyeing polyvinyl chloride fibers are known. Forinstance, there is a dyeing method which comprises preparing aninsoluble complex with an acid dye and a cationic surfactant and usingthis complex for dyeing the fiber; however, none of the conventionalmethods have been able to provide dyed products which are Patented July30, 1974 fully deep in shade. Therefore, a second object of theinvention is to provide a dyeing method by which polyvinyl chloridefibers can be dyed tofully satisfactory deep shades.

Polyacrylonitrile fibers are usually dyed with cationic dyestuffs.However, in this case also, when expansion of the scope of color andwhen the case of dyeing of mixed spun products are considered, theimpartation of dyeability by means of the acid dyes is desirable. Athird object of the present invention is therefore to provide a dyeingmethod which expands the scope of color of the dyed products ofpolyacrylonitrile fibers as well as facilitates the dyeing of mixed spunproducts, especially mixed spun products with wool.

Cellulose acetate fibers are also dyed with disperse dyes as in the casewith polyester fibers, but in this case also the shortcoming was notedthat the brightness of the dyed product was not yet fully satisfactory.A fourth object is therefore to provide a dyeing method which can impartexcellent dyeability to cellulose acetate fibers and dye these fibers tobright shades.

Other object and advantages of this invention will become apparent fromthe following description.

Research was conducted both from the aspect of the modification of thepolyester fiber and the method of dyeing the same. As a consequence, itwas found that shaped articles of certain classes of modified polyesterscould be dyed to exceedingly deep shades when dyed by the anionicdyestuffs in the presence of at least one compound selected from theabove defined sulfonium salts.

The sulfonium salts to be used in the present invention are compoundshaving the hereinbefore indicated formulae. As specific compounds, inthe case, for example, where R, R and R of the foregoing formulae aresaturated hydrocarbon residues, includedare such as thedimethylstearylsulfonium salt, methylethyllaurylsulfonium salt,methylpropyllaurylsulfonium salt, methylbutyllaurylsulfonium salt,ethylpropylstearylsulfonium salt, tributylsulfonium salt,dibutylpropylsulfonium salt and diethylcyclohexylsulfonium salt.

0n the other hand, as examples of unsaturated hydrocarbon residues,there are the alkenyl or the aryl or aralkyl groups such as phenyl,benzyl, naphthyl and naphthylmethyl. For example, mention can be made ofsuch as the dimethylbenzylsulfonium salt, diethylbenzylsulfonium salt,dibutylbenzylsulfonium salt, methylethylnaphthylsulfonium salt,ethylaryllaurylsulfoniurn salt, methylbutyloleylsulfonium salt,ethylpropylphenylsulfonium salt and diarylmethylsulfonium salt.

Further as derivatives of saturated or unsaturated hydrocarbon residues,those hydrocarbon residues having substituents on their side or straightchain are useable. The substituents include such as alkyl, aryl,alkenyl, nitro, alkoxy, halogens, cyancarboxy and sulfonic acid.Needless to say, the substituents are not restricted to those mentionedabove. -As these derivatives, included are such, for example, asdimethyl 4-chlorobenzylsulfonium salt, methylethylZ-methoxybenzylsultonium salt, diethyl 4- methylnaphthylmethylsulfoniumsalt and dibutyl 4-car boxylbenzylsulfonium salt.

0n the other hand, the one other class of sulfonium salts to be used inthis invention is that having the hereinbefore indicated formula Asspecific compounds, included in this caseare such, for example, asfollows:

CzHs

CH3 CH3 CH C 2115 i CH3 0 CH3 CH3 H Polyesters, as used herein, areprincipally intended to be polyethylene terephthalate. However, theexpression polyester also refers to those polyesters which comprise atleast 60 mol percent of ethylene terephthalate units and in which a partof the acid or dihydroxy component is substituted by one or more classesof either difunctional or hydroxy acids such as isophthalic acid,compounds having metal salts of sulfonic acid, betahydroxyethoxybenzoicacid, p-hydroxybenzoic acid, diphenyldicarboxylic acid,naphthalenedicarboxylic acid, diphenylsulfonedicarboxylic acid, adipicacid and sebacic acid, or the aliphatic, alicyclic and aromaticdihydroxy compounds such as diethylene glycol, trimethylene glycol,hexamethylene glycol, neopentylene glycol, 1,4-cyclohexanedimethanol,2,2,4,4-tetramethylcyclobutanediol-1,3, 1,4 bishydroxyethoxybenzene,bisphenol A and compounds having the tertiary amino group [i.e.butyldi(beta-hydroxyethyl) amine]. Further, polyesters in which a minorproportion of a monofunctional compound such as benzoylbenzoic acid and/or a polyfunctional compound of above trifunctional such aspentaerythritol and trimesic acid are copolymen'zed to a certain extentwith substantial crosslinking are applicable. In the preparation ofthese polyesters, the known catalysts and additives such as stabilizers,delustrants, etc., can be added with no trouble at all.

The term modified polyester composition, as used herein, refers to theblended composition of a polyamide and a polyester obtained ashereinbefore described, the blended composition of a polyamide and acopolyester obtained by copolymerizing a polyalkylene glycol with apolyester, the blended composition of a polyester and a polyamide blendcontaining a polyalkylene glycohand the blended composition of apolyester, polyamide and polyalkylene glycol. Modified polyester fiberswhich are particularly desirable include: (a) those obtained bymeltspinning a blended composition of 60-995 wt. percent of a polyesterand 40-05 wt. percent of a polyamide and drawing the resultingfilaments; (b) those obtained'by melt-spinning a blended composition of40-0.5 wt. percent of a polyamide with 60-995 wt. percent of acopolyester obtained by copolymerizing with a polyester 1-35 wt.percent, based on the overall weight of the composition, of apolyalkylene glycol and drawing the resulting filaments; (c) thoseobtained by melt-spinning a blended composition of 99.5-60 wt. percentof a polyester and 0.5-40 wt. percent of a polyamide blend containing,based on the overall weight of the composition, of 1-30 wt. percent of apolyalkylene glycol, and drawing the resulting filaments; (d) thoseobtained by melt-spinning a blended composition consisting of 60-995 wt.percent of a polyester, 0.5-40 wt. percent of a polyamide and 0.6-30 wt.percent of a polyalkylene glycol and drawing the resulting filaments;(e) those obtained by melt-spinning a blended composition of 60-995 wt.percent of a polyester and 40-05 wt. percent of a polyamide and drawingthe resulting filaments, then shrinking the filaments by heat treatingthem and thereafter redrawing the filaments; (f) those obtained bymelt-spinning a blended composition of 60-995 wt. percent ofa polyesterand 40-05 wt. percent of a polyamide, and drawing the resultingfilaments, then shrinking the filaments 2 to 50% at a temperatureranging between C. and the melting temperature of the polyester fiberand thereafter redrawing the filaments; and (g) those obtained bymeltspinning a blended composition of 6099.5 wt. percent of a polyesterand 40-05 wt. percent of a polyamide and drawing the resultingfilaments, followed by shrinking the filaments by heat treating them andthereafter redrawing the filaments at a temperature ranging between roomtemperature and 230 C. and a draw ratio ranging from 2% to the point atwhich breakage of the polyester fiber takes place.

The manufacture of a fiber by melt-spinning and drawing a blendedcomposition of a polyester and some amount of polyamide is known(British Patent Specification No. 610,140). However, the fiber which hasbeen merely melt-spun and drawn in this manner does not demonstratedesirable dyeability when the usual method of dyeing it with anionicdyestuifs is employed. It is only when the fiber is dyed by the dyeingmethod of the present invention that it is possible to provide productsdyed to bright and deep shades so as to be very useful.

As a result of further research with a view to improving the dyeabilityof the fiber itself obtained from the polyester polyamide composition,it was found that when one of the methods of the present invention,i.e., that wherein the fiber formed by melt-spinning and drawing theaforementioned polyester composition is then shrunk 2-50% at atemperature ranging between 140 C. and the melting temperature of thepolyester fiber, and thereafter it is again drawn at a temperaturebetween room temperature and 230 C. and a draw ratio ranging between 2%and the point at which its breakage takes place is employed and the soobtained fiber is used in combination with an anionic dye and at leastone compound selected from the aforementioned sulfonium salts, dyeproducts which are of greater brightness and of deeper shades can beobtained. 'Accordingly, the hereinabove indicated heat treatment andredrawing conditions are both critical. Thus, fibers having excellentdyeability cannot be obtained in those cases where either one of theseconditions are lacking.

Further, ultraviolet absorbents can be used in the dyeing method of thepresent invention for improving the light fastness of the dyed products.The following compounds can be used as ultraviolet absorbents in thepresent invention.

(1) 2-(2-hydroxyphenyl)benzotriazole series, for example, those such asfollows:

N on, N on, /|\N \N- -c1 and \IL/ H \N/ on 0411.

/N\ can N \N/ H 1 I Q- Q- wherein R is H, --C H (wherein n is 1-18),

(where R is alkyl or aryl); and

wherein R is H or SO H.

(3) 2,2'-dihydroxybenzophenone series, for example, those of the formulawherein R is H, C H (wherein 11 1-18),

(where R is alkyl or aryl).

(4) Phenylsalicylic acid series, for example, those of the formula:

II E To-ot g where R is H, C H (where n=1-18),

(wherein R is alkyl or aryl).

(5) Substituted acrylonitrile series, for example, those of theformulas:

0N, RO wherein R is alkyl or aryl.

While the amount of these ultraviolet absorbents used will varydepending upon the class of the material to be dyed, the class of thedyestuff and the concentration and bath ratio etc., the use of about110% (O.W.F.) based on the material to be dyed will do. It is alsopossible to achieve the result desired by imparting the ultravioletabsorbent to the fiber using a separate bath.

Again, the modified polyester composition of the present invention notonly possesses excellent atfinity for anionic dyestuffs, as notedhereinbefore, but also demonstrates satisfactory aflinity for dispersedyes. In addition, it can also be dyed satisfactorily by means of thebasic dyes in the presence of anionic substances. As anionic substances,included are inorganic acids such as sulfuric CN /CN and acetic acidsand the salts thereof; and benzenesulfonie acid, toluenesulfonic acid,higher alkylbenzenesulfonic acid, and sulfuric esters of higher alcoholsand the salts thereof; and phenols.

There are no particular restrictions as to the polyamides to be used inthe present invention as long as they are serviceable with respect totheir thermal resistance, etc. Mention can be made of such, for example,as polycaproamide, polynaphthamide, polyundecamide, polyhexamethyleneadipamide and polymetaxylene adipamide, or c0- polymers of these withother arnide-forming substances. These polyamides can be used eitheralone or in combinations of two or more thereof. Of course, polyamides,the aromatic polyamides such, for example, as those which havecopolymerized therewith the hexamethylene-diammoniurn terephthalatecomponent give especially desirable results with respect tocompatibility. These polyamides are incorporated in the polyester in anamount of 0.540% by weight, and preferably 5 to 35% by weight. If thecontent of polyamide is less than 0.5% by weight, the affinity of theresulting fiber for ionic dyestuffs is inadequate. On the other hand, ifthe content of the polyamide exceeds 40% by weight, the properties as apolyester fiber are lost. Accordingly, it is undesirable for the contentof the polyamide to be outside the range indi cated above.

In addition, the dyeability of the fiber can be further enhanced byincorporating in the foregoing polyesters and/or polyamides in an amountnot exceeding 30% by weight, based on the overall weight of the fiber, apolyoxyalkylene glycol. As the polyoxyalkylene glycol, mention can bemade of such, for example, as polyoxyethylene glycol, polyoxypropyleneglycol, polyoxyethyleneoxypropylene glycol block or random copolymer,methoxypolyoxethylene glycol, phenoxypolyoxyethylene glycol andoctylphenoxypolyoxyethylene glycol. These polyoxyalkylene glycols may bepresent in either the polyester or the polyamide, or in both components.It may be added either during the early stages of the manufacture of thepolyester or during the blending of the components.

It does not matter whether the polyvinyl chloride fiber used in thepresent invention is a homopolymer, a copolymer or an afterchlorinatedproduct.

Good results can naturally be expected even if this method is applied tothe mixed woven products of polyvinyl chloride fiber and other classesof fibers. Moreover, in the case of a mixed spun product of polyvinylchloride fiber with wool, there is a great advantage in that the twofibers can be dyed with the same acid dye in a single bath.

As the polyacrylonitrile fibers to be used in the present invention,acrylic fibers that do not possess dye receptive sites are useable.Included are the Orion (trademark of Du Pont Company) type, Dynel.(trademark of Union Carbide and Chemical Company) type, and the acrylicconjugated fiber. Again, it goes without saying that the presentinvention also has applicability to the mixed textile products of theforegoing fibers with other classes of fibers.

As the cellulose acetate fibers to be used in the present invention,included are the usual diacetate to triacetate fibers. Again, thepresent invention can also be applied to the cellulose acetate fibersobtained by the after acetylation technique. Again, the invention can,of course, be applied to the mixed textile products of the foregoingfibers with other classes of fibers. The method of the present inventionis especially effective in the case of a mixed product of acetate fiberswith polyamide fibers, since both fibers are dyeable with acid dyes.

The modified polyester fibers that can be dyed by means of the method ofthe present invention are the so-called readily dyeable polyester fiberswhose dyeability by means of disperse dyes has been improved, ashereinbefore described, by either an elevated temperature treatment orthe introduction (blending or copolymerizing) of a third component. Theterm readily dyeable polyester fibers, as used herein denote thosefibers having a dye adsorption of at least 60% as determined by themethod of measurement of the rate of dye adsorption as defined below.

The rate of dye adsorption is determined in the following manner. Thespecimen is washed in 100-fold amount of distilled water (70 C.) for 30minutes with stirring, followed by air drying and thorough opening ofthe fiber. One gram of the so standardized specimen is weighed and dyedunder the following conditions:

After completion of the dyeing and cooling to room temperature, asuitable amount of the remaining dye liquor is taken and combined withan equal amount of GP. acetone (reagent), following which thisacetonewater (1:1) mixture is diluted 25 times and the optical densityis measured using a spectrophotometer. Next, the before-dyeing dyeliquor diluted in a similar manner is measured for its optical density.The rate of dye adsorption is then obtained by the following equation,the average of three measurements rounded to whole numbers being used.

Dye adsorption (percent) -5) X 100 wherein d =the optical density of thebefore-dyeing dye liquor and d=the optical density of the after-dyeingremaining liquor.

Polyester fibers having a dye adsorption of below 60% cannot providesatisfactory dyed products even though the method of the presentinvention is used.

If the present invention is applied to polyamide fibers (e.g. nylon) theresults are negative. This is believed to be due to the fact that thedye is not dissociated as a result of the anionic dye forming a complex,with the consequence that in the case of the polyamide fibers having dyereceptive sites the results are negative as a result in the decline inthe dye adsorption.

Further, the anionic dyestuffs, as referred to herein, denote all ofthose dyes having an anionic group, i.e., the acid dyes, direct dyes,metal complex dyes, reactive dyes and acid mordant dyes.

In practicing the present invention, the dyeing methods that can be usedinclude the various conventional methods such as the dip, padding andprinting techniques.

The dyeing conditions will vary depending upon the class and form of thetextile to be dyed and the class of dyeing method to be employed. Forinstance, in the case of the most widely practiced dip method, thedyeing conditions will be as indicated below.

In the case of the method of dyeing the modified polyester fiber, theaforementioned compounds are added to the dye bath in a concentration of1-100% O.W.F. A dyeing temperature of below 100 C. does not result in asatisfactory dye adsorption, therefore, a temperature exceeding 100 C.is required. Usually, the dyeing is carried out at a temperautre of110-130 C. until the intended color deepness is obtained. Again, carrierdyeing can also be carried out effectively using carriers knownconjointly. In addition, it is also possible to make conjoint use of theorganic and inorganic acids or salts in carrying out the dyeingoperation.

On the other hand, in the case of the method of dip dyeing polyvinylchloride fibers, the dyeing may be carried out at 50-100 C. using theaforesaid compounds in a concentration of about 1-50% O.W.F. (percentagebased on the weight of the material to be dyed), though varyingdepending upon the dyestuff used. Again, carrier dyeing can also becarried out effectively using known carriers conjointly. 1

Further, in the case of the cellulose acetate and polyacrylonitrilefibers, the amount of the compounds used will differ depending upon theconcentration of the dyestuff used, but usually the amount ranges from1% to 100%. A dyeing temperature in the range of 80-l20 C. is convenientand, if possible, the higher, the better.

Again, carrier dyeing is also effectively carried out by conjointlyusing known carriers.

As such known carriers, mention can be made of the phenolic compoundssuch as oand p-phenylphenol, the chlorobenzene type compounds such asmonochlorobenzene, o-clichlorobenzene and trichlorobenzene, benzoic acidand benzoic acid type compounds such as benzoic acid, and thenaphthalenic compounds such as methyl naphthalene. These carriers areadded, for example, to the dye bath as an aqueous solution in the caseof those which are water-soluble and as either a dispersion or emulsionin the case of those which are water-insoluble.

For carrying out level dyeing by dispersing the dyestuff thoroughly andfor preventing the formation of tar, it is preferred to use a suitablenonionic surfactant in the method of the present invention. Surfactantssuch as indicated are those which are usually widely used asdispersants. Included are, for example, the polyethylene glycol typesurfactants such as polyethylene glycol alkylamines, polyethylene glycolalkyl ethers and polyethylene glycol aliphatic acid esters, and theether or ester type surfactants which contain the polyhydric alcoholssuch as sorbitan aliphatic acid esters and aliphatic acid'rnonoglycerides as the hydrophilic group.

The textile which has been dyed in accordance with the method of thepresent invention is thoroughly soaped after its dyeing and thereaftersubmitted to reduction clearing, if necessary. The textile dyed by suchmethod still retains adequate fastness even after it has undergone theseafter treatments.

While the particulars of the principle underlying the present inventionare not clear, it is believed that the Water dissolved or disperseddyestuff forms a complex with the sulfonium compounds with the resultthat compatibility and afiinity with respect ot the hydrophobic fibersare created, the complex simultaneously functioning at times as acarrier at elevated temperature to become diffused into the interior ofthe fiber and result in the adsorption of the dye. Accordingly, thebalance of the affinity between the dyestuff and the sulfonium compoundsbecome an important factor that determines the dye adsorption. Theeffects contemplated by the present invention cannot be achieved by justthe insolubilization of the dye but can only be attained, ashereinbefore indicated, in those cases where the specific compoundsdefined by the foregoing formula are used.

Also better dye adsorption is obtained when the pH of the dye bath is onthe acid side.

Next, examples will be given for further illustration of the presentinvention in detail.

EXAMPLE 1 A crepe de chine fabric composed of diacetate fiber, acellulose acetate textile, was dipped in a dye bath of the followingcomposition:

Kayacyl Sky Blue R (0.1. No. 62045) 5% (O.W.F.).

CH; 10% (O.W.F.).

Cribs-S +Br- CZH5 Univadinc W (a nonionic surfactant) 5% (O.W.F.). Bathratio 1:50.

When the dyeing was carried out at 100 C. for minutes, a product dyed toa bright deep shade was obtained. The wet fastness of the resulting dyedproduct was of a degree excelling that obtainable by disperse dyes.

9 EXAMPLE 2 l crepe de chine fabric composed of diacetate fiber wasdipped in a dye bath of the following composition:

Nylomine Yellow AGS 4% (O.W.F.). [C4Hr-?-C4H9] BF (O.W.F.).

Univadine W 4% (0.W.F.). Bath ratio 1:50.

The dyeing was carried out at 80 C. for 120 minutes. After completion ofthe dyeing of the fabric, it was washed in a bath containing an anionicsurfactant, whereupon a product brightly dyed to a deep shade of yellowwas obtained. EXAMPLE 3 As a polyacrylonitrile fiber, Kanekalon wasused. This fiber was dipped in a dye bath of the following composition:

Erlosin Red 2 BX (OJ. No. 26660) 4% (O.W.F.).

C4Hg 10% (O.W.F.). [C Har- S ]*BX CH3 Univadine W 4% (O.W.F.). Bathratio 1:50.

When the dyeing was carried out at 100 C. for 90 minutes, a product dyedto a deep shade of red was obtained.

EXAMPLE 4 Example 3 was repeated except that the dyeing was carried outat 110 C. for 90 minutes using Orlon" instead of the Kanekalon usedtherein. A product dyed to a deep shade of red was obtained.

The modified polyester textile Tetoron T-89 was printed using a paste ofthe foregoing composition. After dyeing the textile, it was steamed at120 C. for 90 minutes. This was followed by water-washing and launderingof the resulting dyed product to obtain a product dyed to a deep shadeof red.

EXAMPLE 6 291 parts of dimethyl terephthalate, 207 parts of ethyleneglycol, 29.1 parts of polyoxyethylene glycol (molecular weight about1500), 0.102 part of calcium acetate monohydrate and 0.75 part ofantimony trioxide were reacted in customary manner to obtain acopolymeric polyester having an intrinsic viscosity 0.45 and a softeningpoint of 252.3C. Fifty grams of this polyester and 10 grams of apolycaproamide of an intrinsic viscosity of 0.38 and a softening pointof 213.7 C., both of which were rendered into particle size havingmaximum diameters 3-5 mm., were mixed together. The mixture was thencharged to an autoclave which was reduced to a pressure below 2 mm. Hgafter having been purged with nitrogen. The temperature was then raisedto 275 C. and by holding this temperature for 30 minutes the twopolymers were thoroughly melted, followed by stirring for 30 minutes.The resulting blend had a softening. point of 249.9 C. This polymer wasspun and the resulting filaments were drawn in customary manner and afiber (3.2 denier) having a tensile strength of 4.2 g./den. and anelongation of 38% was obtained. The dye adsorption was 86.4%.

The third component-contained modified polyester fiber obtained abovewas dipped in a dye bath of the following composition:

Xylene Fast Blue PR (0.1. Acid Blue 129) 4% (O.W.F.).

O NH: A s OaNa V OH:

H l 0 NH -0 CH:

[C12H2sSCHs] Br 10% (O.W.F.).

Unlvadine W 4% (O.W.F.). Bath ratio 1:50.

When the dyeing was carried out at 120 C. for minutes, a product dyedbrightly to a deep shade of blue was obtained.

EXAMPLE 7 An autoclave was charged with 194 parts of dimethylterephthalate, 138 parts of ethylene glycol, 194 parts ofdihydroxypolyethylene oxide-propylene oxide block copolymer (averagemolecular weight about 1700, polyethylene oxide portion about 40 molpercent), 0.068 part of calcium acetate monohydrate and 0.50 part ofantimony trioxide. The autoclave was then gradually heated while slowlyintroducing nitrogen. The temperature was raised to about 230C. over aperiod of about 3 hours while distilling off the methanol formed as aresult of the ester-interchange reaction. After the distillation off ofthe methanol was completed, 0.034 part of phosphoric acid was added as astabilizer and the temperature was raised to 235 C. Stirring was carriedout at atmospheric temperature for 30 minutes at this temperature, afterwhich the pressure of the reaction system was reduced gradually to below0.3 mm. Hg over a period of about 2 hours. The modified polyester had anintrinsic viscosity of 0.50 and a softening point of 258.1 C.

The modified polyester and a copolyamide prepared from caprolactam andhexamethylene diammonium terephthalate were both rendered into granularform having maximum particle diameters from 3 mm. to 5 mm. or less.Fifty parts of this modified] polyester and 5 parts of the copolyamidewere thoroughly mixed and charged to an autoclave. After purging theautoclave with nitrogen, its pressure was reduced to less than 0.2 mm.Hg and the temperature was raised to 275 C. This temperature was heldfor 30 minutes to thoroughly melt the two polymers, followed bystirringfor 30 minutes. The resulting blend had a softening point of255.4" C.

After vacuum drying this polymer at C. for 5 hours, it was spun at 275C. at a spinning speed of 500 meters per minute. The denier fineness ofthe resulting fiber drawn 4.5 X at 80 C. was 2.8, and its tensilestrength was 4.2 g./den. and elongation at break was 42%.

This fiber was dipped in adye bath of the following composition:

12 It was possible to obtain products brightly dyed to deep shades ofblue of Grade 9 using the above.

Xylene Fast Blue PB (G1. Acid Blue 129) 4% (O.W.F.).

10% (O.W.F.).

H -O-OH3CH3C?CH3CHg-O H +(EH55 02H. CH3 CH3 Univadine W 3% (O.W.F.).Bath ratio 1:50.

When the dyeing was carried out at 120 C. for 90 minutes, the fiber wasdyed brightly to a deep shade of blue.

EXAMPLE 8 (a) Preparation of a polyamide-polyoxyalkylene glycol blendSeventy-nine parts of caprolactam, 85 parts of hexamethylenediammoniumterephthalate and 37 parts of polyoxyethylene glycol (average molecularweight about 8000) were dissolved in 40 parts of water and then chargedto a polymerization vessel. After purging the vessel with nitrogen, itwas slowly heated, the water distilling off being removed. Thetemperature of the remaining portion was raised to 270 C. and wasstirred at this temperature for 60 minutes. This was followed bygradually reducing the pressure of the system to 0.77 mm. Hg at whichpressure the polymerization reaction was carried out for 20 minutes. Theasp/m of the resulting polyamide-polyoxyalkylene glycol blend was 1.02.

(b) Preparation of polyester After charging an autoclave with 97 partsof dimethyl terephthalate, 69 parts of ethylene glycol, 0.034 part ofcalcium acetate monohydrate, 0.025 part of antimony trioxide and 0.009part of cobalt acetate, it was slowly heated in a nitrogen atmosphere.The methanol which started to distill off in the neighborhood of 160 C.as a result of the ester-exchange reaction was remoyed to the outside ofthe system via a rectifying column.

The temperature at the time of the completion of the distillation off ofthe methanol was 235 C. To the resulting prepolymer 0.07 part oftrimethyl phosphate was added. The temperature of the system was'raisedto 280 C., stirring was carried out for 30 minutes and thereafter thepressure of the system was reduced to a high vacuum of below 0.2 mm. Hgover aperiod of 1 hours. The asp/c, of the resulting polyethyleneterephthalate was 0.745.

(0) Preparation of polyester composition Forty parts of the aboveprepared polyamide blend and 160 parts of polyethylene terephthalatewere both dried and thereafter melted at 280 C. After blending the twotogether for 20 minutes in a nitrogen atmosphere, the system was reducedto a pressure below 0.5 mm. Hg where it was held for about minutes toeliminate the low boiling components and thus obtain the polyestercomposition.

(d) Dyeing The fiber obtained in customary manner by spinning the soobtained polyester composition following by drawing the resultingfilaments was'dipped in a dye bath of the following composition:

Comparison 1 The case where conjoint use of an assistant'is not usedduring the dyeing.

The polyester fiber obtained by the method of Example 8(a)(b)(c) wasdipped in a dye bath of the following composition:

Acid dye (C.I. Acid Blue 129) 4% (O.W.F.).

Actinol R-100 1 g./liter. Acetic acid 3% (O.W.F.).

When the dyeing was carried out at 120 C. for 9 0 minutes, the fiber wasdyed to only a medium shade.

EXAMPLE 9 Twenty parts of a copolyamide (1 '=0.54) consisting of molpercent of caprolactam and 30 mol percent of hexamethylene-diammoniumterephthalate and parts of polyethylene terephthalate (v =l.05) weremelted at 285 C. under nitrogen for 10 minutes and blended. This blendwas spun at'285 C. in customary manner. The freshly spun filaments weredrawn 43 X by means of an C. pin, then shrunk at a temperature of 230 C.and again drawn 10% at a temperature of C.

The fibers obtained were dyed using a dye bath composed of 4% (O.W.F.)of an acid dye Nylomin Blue GS (I.C.I.) (CI 62055), 5% (O.W.F.) ofacetic acid, 4% (O.W.F.) of nonylphenoxypolyoxyethylene glycol and 4%(O.W.F.) of

and under the conditions of a bath ratio 1:100 and 120 C. 60 minutes,with the consequence that the fiber was dyed to a deep blue shade (Grade8-9).

EXAMPLE 10 Thirteen parts of polyhexamethylene adipamide 7sp./c."= v Iand 87 parts of polyethylene terephthalate (1 '='1.05 were melt-blendedas in Example 9, after which the resulting blend was melt-spun at 285 C.in customary manner. The freshly spun filaments were-drawn 4.25 X bymeans of an 87 C. pin, then shrunk 30% at a temperature of 215 C.- andthereafter again drawn 15% at a temperature of C. I

Actinol R-100 (primary polyoxyethylene lauryl ether) Bath ratio 1gJllter. 1 50.

13 This fiber was dyed using a dye bath composed of 4% (0.W.F.) ofEriosin Red 2BX CI No. 26660 of the formula.

14 The fibers obtained were dipped in a dye bath of the compositionbelow:

The dyeing was carried out at 120 C. for 90 min- OH utes. Aftercompletion of the dyeing operation, soaping of the dyed fiber wascarried out for 30 minutes at 50 N=N--N=N- C. in a 0.2% solution ofMarseilles soap. As a result, a product dyed to a bright shade of bluewas obtained. Al? though this dyed product. was exposed for 40 hours ina Fade-Ometer, there was no fading at all. When, as a OsNB control, aspeciment dyed in a dye of the above composi- Xylene Brilliant Blue 5 GM4% (O.W.F.).

4 0.W.F. [@o oinl-s-cin.o@]+on. s Or CH: CH:

2,2-dihydrotry-4,4-diaeety1benzophenone 4% (O.W.F.).

OH OH 1? l n CHz-C-O- C- -OC-CH| Acetic i 3% (O.W.F.). Bath ratio 1:50.

5% (O.W.F.) of acetic acid, 4% (-0.W.F.) of nonylphenoxypolyethyleneglycol and 4% (0.W.F.) of

11 0-cHicH,s-cHicHro- I 0H- 0H:

and under the conditions of a bath ratio 1:100 and 120 C. 60 minutes,thereby obtaining a product dyed tion but from which2,2'-dihydroxy-4,4-diacetylbenzophenone was eliminated was similarlyexposed for 40 hours in a Fade-Orneter, marked fading was noted.

EXAMPLE '13 The polyvinyl chloride fiber Valren was dipped in a dye bathof the following composition:

to a deep red Shade (Grade 0 Xylene Fast Blue PR 0.1. Acid Blue 129 2%own 1 1 [C4H90CHaCHr-S-CHzCHzOC4HOH'CzH5SOF 5% (0.W.F.). Tetoron T-89 (apolyester fiber) was dyed at 130 C. for 90 minutes in a dye bath of thefollowing compo- Univadme w 2% (0W1), sition; B81311 r8110 1250.

Xylene Fast Blue PR (C.I. Acid Blue 129) 1% (O.W.F.). 1% (O.W.F.).OC2H4?C2H|O +CHgS Or CH: CH;

OH OH i ii 11 CHa-C O- C O C-CH:

(2,2-dih dro -44-diacetylbenzo henone) 27 (O.W.F.). Acetic Jd xy p 2%0.w.r.

(O.W.F.). P.P.P. OH Bath ratio 1: 100.

When soaping was carried out for minutes at 60 C. in a 0.2% solution ofScourol after completion of the dyeing operation, a product dyed to abright shade of blue was obtained. When this dyed product was exposedfor hours in a Fade-Ometer, no fading was observed at all. When, as acontrol, a specimendyed in a dye bath of the above composition but fromwhich the 2,2'-dihydroxy- 4,4'-diacety1benzophenone was eliminated, wassimilarly exposed for 40 hours in a Fade-Ometer, marked fading occurred.

EXA'MPIJE 1=2 The temperature of the bath was then slowly raised and thedyeing was carried out at 100 C. for 60 minutes, whereupon a productbrightly dlyed to a deep shade (Grade 8-9) of blue .was obtained. Thecolorfastness to light and washing of the resulting dyed product wasvery excellent. The dye adsorption was The polyvinyl chloride fiberVzalren was dipped in a dye bath of the following composition:

Suminol Fast Red B (6.1. No. 14680) 3% (0.W.F,.). [CzHsOCHzCHr-S-CHzCHn0C7H5] CH:S0(' 3% (0.).

( lHa 7 tiiiilifl i?0.'

The temperature of-the bath was then slowly raised and the dyeing wascarried out at C. for 60 minutes to yield a product dyed to a brightdeep shade (Grade 8-9) of blue. The colorfastness to light and washingof the so obtained product was very outstanding. The dye adsorption was80%.

EXAMPLE 15 EXAMPLE 21 The polyvinyl chloride fiber Valren was dipped ina per y bath of the followmg composmon: Kayacyl Sky 131 R 31, 2045 2 5Thiodiethyleue glycol 2 [041100CHgCHrS-CHzCH5OC4Hn] CzH5S 04" 4 3H5 Vsumjno Fast Red B 14680) 3% Indalca ABV (12%) (a paste consistingpredominately oflocust 0,1150ontoHr-s-omcmo-mmromsm- 3% (ow-F0. 35 f ff33 Ha Total 10o Trichlorobenzene (carrier) 3 g./li ter. atillitififl::::::::::::::::::::::::::::::::::::::: tie A crepe de chinefabric of diacetate fiber was Printed using a paste of the foregoingcomposition. After drying 15 the printed fabric, it was steamed at 100C. for 40 minutes. The so obtained dyed fabric was then waterwashed andlaundered, whereupon a product which was The temperature of the bath wasslowly raised and the d d t a d h d f bl was bt i d dyeing was carriedout at 90 C. for 60 minutes, where- I upon 'a product dyed to a brightshade (Grade 9-'10) of EXAMPLE 22 red was obtained. The dye adsorptionwas 95%. The modified polyester fiber Tetoron" T-89 was dipped in a dyebath of the following composition:

EXAMPLE 16 Th d d 60 C f 60 t Lissamine Fast Violet 2 BS (C.I. No.62020) 4%(0.W.F.),

e eing was carrie out at or minu es 25 Tevilon was used instead ofValren. A product dyed 2 to a bright shade of red was obtained.UnivadineW 4%(O.W.F.).

Sulfuric acid. 1 gJliter.

EXAMPLE -17 When the dye ng was carried out at 120 C. for 2 The dyeingWas carried out at 100 C. for 60 minutes hours, a product dyed to a deepshade of violet was as in Example 14 except that a metal-containingdyeobtained. stuif Kayakalan -Red 2BL was used instead of the dye- Whatis claimed is: stufi used in Example 14, with the result that aproduct 1. A method of dyeing a textile fiber selected from the dyed toa deep shade of red was obtained. group consisting of modifiedpolyester, polyvinyl chloride,

polyacrylonitrile, and cellulose acetate fibers, which com- EXAMPLE 1'8prises dyeing the fibers with an anionic dyestutf in the presence of atleast one compound selected from sulfo- The dyeing was carried out at 90C. for 60 minutes m Salts f the f l as in Example 15, except thatinstead of the dyestutf R used therein a reactive dye Remasole Red B wasused, 1

. I with the result that a product dyed to a deep shade of n 4- i] redwas obtained. wherein R, R and R are each selected from the groupEXAMPLE '19' consisting of alkyl, alkenyl, cycloalkyl, aryl and aralkylgroups of 1-l8 carbon atoms, R and R are each alkyl A crepe d6 Chinefabric composed of dlacetate fiber, 3 groups of 1-5 carbon atoms and Xis selected from the Cel ulos atletate textile, Was pp in y bath 0f thegroup consisting of halogens, alkoxy sulfate and OH followingcomposition: group.

Kayacyl Sky Blue R (0.1. NO- 62045) 5% (0.W.F.).

041190 CHzCHr-?CHzCHz0-C4Hn] C21-I5S O4" oz a Univadlne W-...' 5%(O.W.F.).

Bath raiio 1:50.

AS a result, a Product y I0 3 P Shade of blue 2. The method of claim 1wherein said sulfonium salt is was obtained.

[EXAMPLE 20 H OC2H4SCZH4O A mixed woven fabric composed of 6 nylon anddi- (IDHB I :l CH3S0 acetate fibers was dipped in a dye bath of thefollowing composition:

Kayaeyl Sky Blue R (0.1. No. 62045). 4% (O.W.F.)-

CH SOt- 10% (O.W.I l: -OCHaCH;--?CH2CH:O

Univadine W. 4% ().W.F.). Soda Ashu 1 gJhter. Bath ratio... 1:50.

3. The method of claim 1 wherein said sulfonium salt is I When thedyeing was carried out at 100 c. for -cm mcicmomo@:l CHbSOr 15 minutes,a product dyed to a bright shade of blue and I being excellent in soliddyeing property was obtained. CH3 CH1 3,826,609 17 18 4. The method ofclaim 1 wherein the sulfonium salt is tained by melt-spinning a blendedcomposition of 60 [O2H5OCHaCH2 S CHflCHZ0 G2H5]+CHsS t0 WBIg ht ofpolyester and t0 I weight of polyamlde, drawing the resulting filaments,followed by shrinking the filaments 2% to 50% of 5. The method of claim4 wherein the textile fiber is 5 their initial length by heating thefilaments at a tema modified polyester selected from the groupconsisting of: pemmre i hi th range f 140 C, d th melting that Obtainedy melt-Spinning a blended positemperature of said polyester filamentsand thereafter tion of 60 to 995% by Weight of Polyester and 40 t0redrawing the filaments; and (g) that obtained by 05% y Weight ofPolyamide and drawing the resultmelt-spinning a blended composition of60 to 99.5

ing filaments; (b) that obtained by melt-spinning a by weight ofpolyester and 40 to 0.5% by weight of blended composition of 40 to 0.5by weight of polypolyamide, drawing the resulting filaments, followedamlde Wltb 60 i0 995% by Welgbt of a l y by heat treating and shrinkingthe filaments, and

thereafter again drawing said filaments at a rate of elongation rangingfrom 2% of their initial length to obtained by copolymerizing with apolyester 1 to 30% by weight, based on the overall weight of thecomposition, of a polyoxyalkylene glycol, and drawing the resultingfilaments; (c) that obtained by meltspinning a blended composition of99.5 to 60% by weight of polyester and 0.5 to 40% by weight of apolyamide blend containing, based on the overall weight of thecomposition, 1 to 30% by weight of a the point at which breakage of saidpolyester filaments takes place, at a temperature within the range ofroom temperature and 230 C.

References Cited UNITED STATES PATENTS polyoxyallcylene glycol, anddrawing the resulting filaments; (d) that obtained by melt spinning ablended 3,251,642 5/1966 Mackenzle et a1 X composition of 60 to 99.5% byweight of polyester, 3,567,366 3/1971 Sand at 8 173 0.5 to 40% by weightof polyamide and 0.6 to 30% by 2,123,740 7/ 1938 q y X 3,666,403 5/ 1972Shunauchi et al 8--l72 weight of polyoxyalkylene glycol and drawing theresulting filaments; (e) that obtained by meltspinning a blendedcomposition of 60 to 99.5% by weight of polyester and 40 to 0.5% byweight of polyamide, drawing the resulting filaments, followed by heattreating and shrinking the filaments, and thereafter again drawing thefilaments; (f) that ob- THOMAS J. HERBERT, 111., Primary Examiner US.Cl. X.R. 8-21 B, 21 C, 173

